Stabilized diazo-type sensitive material



- component.

Patented Apr. 24, 1945 UNITED '-\STATES PATENT oFri-c STABILIZEDDIAZO-TYPE SENSITIVE MATERIAL No Drawing. Application December 4, 1942,Serial No. 467,902

13 Claims.

This invention relates to the stabilization of light-sensitive layerswhich are produced by the incorporation of a diazo compound as thelightsensitive medium onto the surface of a suitable carrier base. 7More particularly, it refers to the stabilization of so-called d'rydevelopment diazotype light-sensitive layers wherein the diazo compoundis a diazo compound derived from ortho or para aminonaphthol or fromN-monoor di-substituted aromatic para-diamines, which diazo compound isincorporated into the light-sensitive' layer, together with an azodyestuff coupling Various processes are known for the preparation oflight-sensitive layers which depend upon the use of a diazo compound asthe light-sensitive medium, and various materials have been employed forthe carrier of the light-sensitive with the diazo compound, thedevelopment of the.

dyestufl forming the image is eilected by bringing the exposedlight-sensitive layer into contact with.

ammonia gas. This is known as the ing process. v

The dyestuflf components, as applied on the carrier, are relativelyunstable and cannot be stored for long periods prior -to use. Thelightdry developsensitive layers which carry the coupling component aswell as the diazo compound in the light-sensitive layer are subject topremature.

coupling of the said dyestufl components as well as decomposition of thediazo compound upon long storage. Many attempts have been made to obtainmore stable coating solutions and to render the light-sensitive layersproduced therefrom less sensitive todeterioration without imcompoundupon which the production of 'aocu- The sensitized pairing thelight-sensitive qualities of the diazo rate images from the originaldepends. These attempts have hitherto been relatively unsuccessful. Itis therefore the object of this invention to provide coating solutionsand light-sensitive layers, using diazo compounds as the lightsensitivemedium which can be stored for long periods prior to use and will bestable during storage even under unfavorable conditions.

I have found that coating solutions and. the

10 light-sensitive layers prepared therefrom can be stabilized againstdecomposition of the lightsensitive materialand premature coupling ofthe dyestufl components by adding to the coating solution a compound ofthe following class: saturated and unsaturated gamma lactones of thefollowing general formulae:

I g O X\ ZI Y o o-a Y l 0 H =o so X Y l n 40 o BIC- 0 H: C V a 11.

wherein X is a member of'the group consisting of H, OH, COOH and alkyl,Y is a member of the group consisting of H and alkyl, Z is a. member ofthe group consisting of H and OH, R is a lower alkyl radical, this amember of the group consisting of H and COOH, and All; means alkylene.

Examples of such compounds are: 1. Gamma-valero lactone Gamma-valerolactone -y -carbonic acid HaC- mo coon 3. 'y-Dihydroxy lactone of thegamma-hydroxy crotonic acid 4. 'y-Dihydroxy lactone of the gamma-hydroxyp-methyl crotonic acid OH. OH

. a-Angelica lactone 6. p-Angelica lactone Example!2.1-diazo-hydroxy-naphthalenesulfonic acid "parts... 14.0 Concentratedhydrochloric acid parts by volume- 7.0 Nickel sulp j arts" 31.5Phloroglucine do 4.9

Thiourea 'do' .200

The following are dissolvedin 1000 cc. of water. To this coat-' I ingsolution there are added 10.2 grams of gamma valero lactone per liter.This solution is then spread on paper, fabric, film or the like by the vusual coating method for the production of diazo type light-sensitivelayers, using a doctor blade to insure a thin even coating. Afterstorage at room temperature for several months, the stability of thesensitized material containing the gamma valero lactone was tested byexposing a. test piece to light under a suitable diapositi've anddeveloping the image by application of ammonia gas. The resulting imagereproduced on the light-sensitive layer containing the gamma valerolactone was compared with the image reproduced under the same conditionson a light-sensitive layer made from the same coating composition butcontaining no gamma valero lactone which latter had been stored underthe same conditions for the same length of time. The background andconsequently the contrast of the image reproduced on thelight-sensitivelayer made in accordance with this example is superior to that of thesample which doesnot contain the gamma valero lactone in thelightsensitive layer.

' Example II v The composition of the coating solution is the same as inExample I but as a stabilizer 13.4 grams of gamma valero lactone 'ycarbonic acid per liter are used instead of the gamma valero the aboveclass show greatly improved solution not containing a gamma lactonestabil- 'coating made from a solution gamma lactone stabilizer.

v ing, storage lactone. The coating, storage and testing procedures arethe same as in Example I. The stability of the coating made according tothis example was found to be superior to that of a Example III Thecomposition of the coating solution is the same as in Example I but as astabilizer 10.4

grams of the 'y di-hydroxy lactone of gamma-.

hydroxy crotonic acid per liter are used instead of the gamma valerolactone. The coating, storage and testing procedures are the same as inExample I. The stability of the coating made according to this examplewas found to be superior to that of a coating made from a solutionnotcontaining a gamma lactone stabilizer.

Example IV The composition of the coating solution is the same as inExample I but as a stabilizer 11.8 grams of the 'ydi-hydroxy lactone ofgammahydroxy betamethyl crotonic acid per liter are used instead of thegamma valero lactone. The coating, storage and testing procedures arethe same as in Example I. The stability of the coating made according tothis example was found to be superior to thatof a coating made from aizer.

Example V I The composition of the coating solution is the same as inExample I but as a stabilizer 8.7 grams of alpha-beta-angelica lactoneare used instead of the gamma valero lactone. The coatand testingprocedures are the same as in Example I. The stability of the coatingmade according to this example was found to be superior to that of acoating made from a solution not containing a gamma lactone stabilizer.

not containing a- Example v1 I Parts Zinc chloride double salt of thediazo-compound obtained from N-ethanol-ethyl are dissolved in 1000 cc.water. To this solution there are added 10.2 grams of. gamma valero ofthe gamma valero lactone. The coating, storage and. testing proceduresare the same as in Example VI. The stability of the coating madeaccording to this example was found to be superlor to that of a coatingmade from a solution not containing a Eamma lactone stabilizer.

amino-i-aminobenzene 10.5 Citric acid I i l I 50.02.3-dihydroxy-naphthalene 5.9

Thiourea 45.0 The sodium salt of the naphthalene-1.3.6

trisulfonic acid 32.5 Aluminum sulphate 6.9

Example X The composition of the coating solution is the same as inExample VI but as a stabilizer 8.7 grams of alpha-beta-angelica lactoneper liter are used instead of the gamma valero lactone.

lactone per liter. The solution is then spread on a suitable base, suchas paper, fabric, fllm or the like by the usual coating method in thesame manner as described in Example I. The lightsensitive layer thusproduced is then stored at room temperature for several months and itsstability is then tested by observing the appearance of color in thelight-sensitive layer due to premature coupling of the dye componentsand by comparison of its light-sensitive qualities with those of a testsample prepared and treated in the same manner as thelight-sensitivelayer of this example but omitting the gamma valerolactone stabilizer. When so tested, it was found that thelight-sensitive layers made in accordance with this example show anegligible amount of coloring due to premature coupling of the dyecomponents after the storage period, whereas,

light-sensitive layers made from the same solu-. tion but not having thegamma valero lactone stabilizing agent, under the same conditions, showa considerable amount of coloring due to premature coupling. It also wasfound that upon ex osure to light under a suitable diapositive and Thecoating, storage and testing procedures are the same as in Example VI.The stability of the coating made according to this example was found tobe superiorto that of a coating made from a solution not-containing agamma lactone stabilizer.

Various changes may be made in the details 0 of my invention asdescribed in the foregoing development of the image by application ofa'mmonia gas, the light-sensitive layers of this example produce imageshaving better definition and less background color than dolight-sensitive layers not having the gammavalero lactonestaspeciflcation within the, scope of the claims appended hereto withoutsacrificing the advantages of my invention.

. Example XI Parts Zinc chloride double salt of the diazo-compoundobtained from N-mono-ethyl- To this solution there are added 10.2 gramsof gamma valero lactone per *liter. The coating. storage and testingprocedures are the same as in. Example I. The stability of the coating,made 40 according to this example was found to be superior to that of acoating made from a solution bilizlng agent, but'otherwise having beenmade and treated the same as thelight-sensitive layer of this example.

Eeample VII The composition of the coating solution is the same asinExample VI but as a stabilizer 13.4 grams of gamma valero lactone 'ycarbonic acid per liter are used instead of the gamma valero lactone.The coating. storage and testing pro cedures arethe same as in ExampleVI. The

stability of the coating made'according to this example was found to besuperior to that of a gamma lactone stabilizer.

, Example v11: v The coating composition is the same as in Example VIbut as a stabilizer 10.4 grams of the coating made from a solutionnotcontaining a di-hydroxy' lactone of Bamma-hydroxy crotonic acid perliter are used instead of-the gamma valero lactone. The coating, storageand testing procedures are the same as in Example VI.

not containing a gamma lactone stabilizer.

Example XII Zinc chloride double salt of the diazo-compound obtainedfrom N-ethanol-ethylamino-4-aminobenzene 10.5 Citric acid .j 5 Thiourea45 The sodium salt of the naphthalene 1,3.6-- 32.5

, trisulfonic acid The aluminum sulfate are dissolved in 1000 cc.of-water 8.9

To this solution there areadded 10.2 of

gamma valero lactone per liter. The solution is then spread on asuitable base, such as paper, fabric, film or the like by the usualcoating method in the same manner as described in Example I. Thelight-sensitive layer thus produced is then stored at room temperature.for

' several months and its stability is then tested by,

4 The stability of the coating" made according to this example was foundto-be superior to that 4 of a. coating made from a solution notcontaining a gamma lactone stabilizer. a

Example IX The coating compositionis the same as Example VI but as astabilizer 11.8 grams of the I di-hydroxy lactone of gamma-hydroxybetamethyl crotonic acid per liter are used instead observing theappearanceof color in the light-.- sensitive layer due to decompositionof the diazo-.

compound and by comparison with that of atest j sample prepared andtreated in the same manner as the light-sensitive layer of this examplebut omitting the gamma valero lactone. The test pieces are then exposedto light under a suitable diapositive and the images developed byappli-'' cation of an alkali solution of a suitable azo-' component suchas phloro-glucine resorclne, or 2 3 dihydroxy naphthalene. The resultingimage reproduced on the light-sensitive layer,

containing the gamma valero lactone showed a 4 r higher color contrastof the image indicatingthe prevention of the decomposition and theconsequent discoloration of at storage. v

I claim:

1. The process oi increasing the stability of a diazo-typelight-sensitive layer containing a suitthe diam-compound whileable'diazo compound which comprises adding to the coating solution amember the class consisting of saturated and unsaturated gamma lactonesof the following formulae: I

and

wherein X is a member of the group consisting of H, OH, COOH and alkyl,Y is a member of the group consisting of H and alkyl, Z is a member ofthe group consisting of H and OH, R is a lower alkyl radical. R1 is amember of the. group which comprises adding to thecoating solution amember of the group consisting of saturated and unsaturated gammalactones of the following formulae:

wherein X is a member of the group consisting of H, OH, COOH and alkyl,Y is a member of the group consisting of H and alkyl, Z is a member ofthe groupconsisting of H and 0H,"R is a lower alkyl radical, R1 is amember of the group consisting of H and COOH, and Alk means alkylene;and coating a suitable base with said solution.

3. The process of increasing the stability of a dlazo-typelight-sensitive layer containing a diazo compound derived from a paraamino aniline compound and an azo dye coupling component and produced byapplying to a suitable base a coating solution containing said diazocompound and said azo dye component, which comprises adding to thecoating solution a member of the group consisting of saturated andunsaturated gamma lactones of the following formulae:

wherein X is a member of the group consisting of H, OH, COOH and alkyl,Y is a member of the group consisting of H and alkyl, Z is a member ofthe group consisting of H and OH, R is a lower alkyl radical, R1 is amember of the group consisting of H and COOH, and Alk means alkylene;and coating a suitable base with said solution.

4. The process of increasing the stability of a diazo-typelight-sensitive layer containing a diazo compound derived from an orthoamino naphthol compound and an azo dye coupling component and producedby applying to a suitable base a coating solution containing said diazocompound and said azo dye component, which comprises 2,374,563 l addingto the coating solution a member of the the group consisting ofsaturated and unsaturgroup consisting oi saturated and unsaturated atedgamma lactones of the following formulae:

gamma lactonesof the following furmulae: 0 y

0 Y-C-C v y-c-ik p o Y 70/ Y- -c Y a i z a at z 1 Y\ E .Y o (ic- Y/ o Yi o n H 1':

x Y 0 Y\ a Y):- Y-C---C- l Y 0 a Y Aik iiik and a and o ,0 I i Bic-( 1 v0 11, -0 80 a R, R

wherein x is a member of the group consisting wherein X is a member ofthe group onsistin or H, OH, COOH and alkyl, Y is a member of the of H,OH, 000K, and alkyl, Y is a membe of group consisting of H and alkyl Zis a member of .the group consisting f E n l. Z i a .1 the groupconsisting of H and OH, R is a lower be 0! thegmllp consisting of H a dOH R 15 11 alkyl radical R1 is a member of the grou 4 p conlower alkylradical, R1 s 8 member of the 8 sisting of H and COOI-l, and Alk meansalkylene.

consisting of H and COOH, and means a y- 9. Light-sensitive layers on asuitable base gene; and coating a suitable base withsaid solu--comprjsing a diam compound t i from a on. i I

5.The process or increasing he s il of a pling component and a member orthe grou diamyp fight-Sensitive lay r aining a diam consisting ofsaturated and unsaturated gamma compound obtained from an ortho aminnaphlactones of the following formulae: Y

' ponent and produced by applying a coating soluthol compound and an azodye coupling com- 0 tion containing said diazo compound and mo dyecomponent on a suitable base, which comprises adding gamma valerolactone to the coat- Y ing solution-and coating a suitable base withsaid solution. h I X Z 6. The process of increasing the stability of a 0dlazo-type light-sensitive layer containing a diazo a compound obtainedfrom a para aminoaniline a, compound and an azo dye coupling component Y0 and produced by applying a coating solution coni taining said diazocompound and azo dye comi l ponent toa. suitable base, which comprisesaddin! Eamma'valero lactone '7 carbonic acid tothe Y c coatingsolution'and coating a suitable base with and produced by applyingacoating solution V prises adding the gamma-di-hydroxy lactone of a 'Tsaid solutiona Y 60 'l. The process of increasing the stability of adiam-type light-sensitive layer containing a diazo Y compound obtainedfrom a para amino aniline. compound and an azo dye couplingcomponent Hcontainingsaid diazo compound and said azo and dye component to asuitable base, which comthe gamma-hydroxy crotonic acid to the coatingsolution and coating a suitable base with said solution.

8. light-sensitive layers as a suitable base R1 i i comprising a diazocompound suitable for formwherein X is a member of the group consistinging a stable two component diazo-type layer, an of H; OH, COOH andalkyl, Y is a member of the azo dye coupling component and a member of76 group consisting of Hand alkyl, Z is a inember of para amino anilinecompound, an azo dye couthe group consisting of H and OH, R is a loweralkyl radical, R1 is a member of the group con-. sisting of H and COOH,and All: means alkylene.

10. Light-sensitive layers on a suitable base and 0 H inc-0 '/O m '-cwherein X is a member of the group consisting of H, OH, COOH and alkyl,Y is a member of the group consisting of H and alkyl, Z is a member ofthe group consisting of H and OH, R is a lower alkyl radical, R1 is amember of the group consistingv of H and COOH, and Alk means alkylene. va

11, Light-sensitive layers on a suitable base comprising a diazocompound obtained from an ortho amino naphthol compound, an azo dyecoupling component and gamma valero lac ne.

12. Light-sensitive layers on a suitable ase comprising a, diazocompound obtained from a para amino aniline compound, an azo dyecoupling component, and gamma valero lactone 'y carbonic acid.

13. Light-sensitive layers on a suitable base comprising a diazocompound obtained from a para amino aniline compound, an azo dyecoupling component and the 'y di-hydroxy lactone of gamma-hydroxycrotonic acid.

MAXmm-IAN K. REICHEL.

